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Authors: Sietmann, Jan
Tenberge, Marius
Wahl, Johannes M.
Title: Wacker oxidation of methylenecyclobutanes : scope and selectivity in an unusual setting
Online publication date: 1-Mar-2024
Year of first publication: 2022
Language: english
Abstract: Methylenecyclobutanes are found to undergo Wacker oxidation via a semi-pinacol-type rearrangement. Key to a successful process is the use of tert-butyl nitrite as oxidant, which not only enables efficient catalyst turn-over but also ensures high Markovnikov-selectivity under mild conditions. Thus, cyclopentanones (26 examples) can be accessed in an overall good yield and excellent selectivity (up to 97 % yield, generally >99 : 1 ketone:aldehyde ratio). Stereochemical analysis of the reaction sequence reveals migration aptitudes in line with related 1,2-shifts. By introducing a pyox ligand to palladium, prochiral methylenecyclobutanes can be desymmetrized, thus realizing the first enantioselective Wacker oxidation.
DDC: 540 Chemie
540 Chemistry and allied sciences
Institution: Johannes Gutenberg-Universität Mainz
Department: FB 09 Chemie, Pharmazie u. Geowissensch.
Place: Mainz
Version: Published version
Publication type: Zeitschriftenaufsatz
Document type specification: Scientific article
License: CC BY
Information on rights of use:
Journal: Angewandte Chemie International Edition
Pages or article number: e202215381
Publisher: Wiley
Publisher place: Weinheim
Issue date: 2022
ISSN: 1521-3773
Publisher DOI: 10.1002/anie.202215381
Relations: is version of 10.25358/openscience-10142
Appears in collections:DFG-491381577-H

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